Water-soluble reactive dyes containing halopyrimidine-5-carboxamido groups



of the aforestated meanings,

United v Statesv Patent 3 342 797 WATER-SOLUBLE REAcTivE DYES CONTAININGHALOPYRIMIDINE-S-CARBOXAMIDO GROUPS Jacques Guenthard, Binningen,Basel-Land, Switzerland,

assignor to Sandoz Ltd., (also known as Sandoz A.G.), Basel, SwitzerlandNo Drawing. Filed Sept. 28, 1964, Ser. No. 399,899 Claims priority,application Switzerland, Oct. 4, 1963,

12,266/ 63 8 Claims. (Cl. 260-146) This invention relates towater-soluble reactive dyes of wherein each of A and A represents ahydrogen atom, the radical of a water-soluble dye oran alkyl radical,preferably a lower alkyl radical, which may be substituted byhydroxy,lower alkoxy, carboxylic acid or sulfonic acid groups or an aromaticcarbocyclic at most binuclear radical which may be substituted byhydroxy, lower alkyl, lower alkoxy, carboxylic acid or sulfonic acidgroups, A and A being identical or different from each other, but atleast one of them being the radical of a water-soluble dye,

R represents hydrogen or an unsubstituted or substituted lower alkylradical,

R represents hydrogen or an unsubstituted or substituted lower alkylradical,

hal represents chlorine or bromine, and

Z represents hydrogen, chlorine, bromine or methyl which may besubstituted either by chlorine or bromine.

The process for the production of the new watersoluble reactive dyesconsists in reacting 1 mole of a compound of the formula N E 1-1IT- O C--hal .hal (II) wherein E represents a hydrogen atom or the radical of awater-soluble dye, or of an organic compound which may be capable of dyeformation and hal and Z have one with 1 mole of a compound of theformula Eq-N-H 1's, (III) wherein E represents a hydrogen atom or theradical of a'water-soluble dye, or of an organic compound which may becapable of dye formation and R has one of the aforestated meanings. Inthese formula E and E maybe identical, but at least one of the twomust-stand for the radical of a water-soluble dye or of a compoundcapable of dye formation. When E and E or both E, and E represent aradical or radicals of a compound capable of dye formation, the reactionproduct is converted into a water-soluble dye by azo coupling orcondensation.

The reaction of the compounds of Formula H with those of Formula III iseffected preferably in an aqueous or aqueous-organic medium :at a weaklyacid, neutral or weakly alkaline reaction, i.g. in the pH range of 4 to10,

and at a low or moderately high temperature, e.g. 050

C., or preferably -30 C. In general, approximately one mole of acompound of Formula H is employed to each mole of an amino for acylationof the dyes or the intermediates. The halogen halide formed isneutralized with an acid-binding agent, added either at the commencementof the reaction or in small portions during its course. Suitable agentsfor this purpose are sodium acetate, sodium carbonate and bicarbonate,sodium tetraborate, trisodium phosphate and sodium hydroxide in powderform or in concentrated aqueous solution. Potassium or lithium salts canbe used as alternatives to sodium salts. The addition of small amountsof a wetting or emulsifying agent can accelerate the rate of reaction.When a purely organic medium is employed it is of advantage to add tothe reaction mixture a tertiary amine to act as acid-binding agent, e.g.dimethylor diethyl-aminobenzene, pyridine or a mixture of pyridinebases.

The starting dyes of Formula II may belong to different classes. Theymay be, for instance, monoazo dyes, e.g. of the typebenzene-azo-pyrazolone, polyazo dyes, e.g. of the typebenzene-azo-'benzene-azo-naphthalene, anthraquinone dyes, e.g. of thetype 1 amino 2 sulfo 4- (m-ononuclear) arylamino-anthraquinone,phthalocyanine dyes, e.g. of the type copper-phthalocyanine-trisulfonicacid, nitro dyes, e.g. of the type 2-nitro-1,l'-diphenylamine-4-sulfonicacid-phenylamide, or formazane dyes, e.g. the copper complex compound ofthe dye N,N-bis- [2-hydroxy 4-(2'-carboxy phenylaminosulfonyl)phenyl] ms(4" amino 2",5" dimethoxyphenylsulfonyl)- formazane.

The azo dyes may be metal-free, metal-containing, nonmetallizable, ormetallizable, e.g. suitable for complexing with chrominum or coppercompounds. Particularly suitable metal-containing dyes are the 1:1copper, 1:1 nickel, 1:2 chromium and 1:2 cobalt complex dyes.Phthalocyanine dyes, when used, may contain the usual metals as centralatoms, e.g. copper, cobalt or nickel.

The preferred starting dyes of Formula II are those having at least onebut generally not more than three or four salt-forming,water-solubilizing groups. The principal groups of this type are thesulfonic acid, carboxylic acid, sulfuric acid ester and sulfonic acidamide groups,'of which the last-named may be acylated. They are normallylinked to the base molecule of the dye or to a hydrocarbon radical boundto that molecule.

Similarly, the dyes of Formula III can be chosen from dilferent classes,e.g. the mono-, or poly-azo, anthraquinone, nitro, formazane orphthalocyanine series. The azo dyes also may be metal-free,metal-containing, nonmetallizable or metallizable. The phthalocyaninesmay contain as central atoms the usual metal atoms, e.g. copper, cobaltor nickel. The preferred dyes of Formula III are those having at leastone but generally not more than three or foursalt-forming,water-solubilizing grOups. The principal groups of thistype are the sulfonic acid, carboxylic acid sulfuric acid ester andsulfonic acid amide groups, of which the last-named may be acylated.They are normally linked to the base molecule of the dye or to ahydrocarbon radical bound to that molecule. When the substituents R andR are unsubstituted or substituted alkyl radicals they containpreferably 1 to 5 carbon atoms and are, e.g., methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-hydr-oxyethyl, 2- or 3-hydroxypropyl, 2 ethoxyorZ-methoxy-ethyl, 2- or 3-methoxypropyl or 2- chlorethyl. They can alsobe a benzyl or phenylet-hyl radical.

The groups NH NOC -hal and l hal may occupy any of the positions of thedye molecule. In azo dyes, for instance, they can be present in thediazo component or the coupling component, or in the case of disazo dyesin the central component; in anthraquinone and phthalocyanine dyes theycan be bound directly to the dye molecule, i.e. on the anthraquinone.nucleus or the benzene nuclei of the phthalocyanine molecule. But is ispreferable for these groups to be present on a substituent of the basemolecule, for instance in phthalocyanines on an aliphatic or aromaticradical bound through a sulfonic acid amide group to a benzene nucleusof the phthalocyanine molecule, e.g.

and in anthraquinones on a phenyl, phenylaminophenyl, diphenyl,phenoxyphenyl or phenylthiophenyl radical.

l,4-diaminoanthraquinones having at least one amino group substituted byone of the aforenamed radicals are particularly suitable. Theanthraquinones may contain further substituents in the nucleus, e.g.halogen atoms or hydroxyl, lower alkylsulfonyl, e.g. methylsulfonyl,arylsulfonyl, e.g. phenylsulfonyl, hydroxyphenyl, alkoXyphenyl, e.g.methoxyphenyl, or phenoxy groups; dyes of other chemical classes can besimilarly substituted. Thus the azo, anthraquinone and phthalocyaninedyes and dye intermediates containing amino groups which are disclosedin French patent specification 1,247,660 and the dyes disclosed in Swisspatent specification 359,228, pages 1 to 6, are suitable for theproduction of reactive dyes according to the present invention.

Examples of suitable compounds of Formula (II) are the dyes described inthe examples of US. patent application Ser. No. 364,306; filed May 1,1964, and Belgian patent No. 645,855.

The following are enumerated to exemplify suitable compounds of formulaeE-NH and Ez-IITH Aminocarboxylic acids such as aminoacetic acid, N-methylaminoacetic acid, aor fi-aminopropionic acid, ocamino butyricacid, a-amino-iso-valeric acid, 2-, 3- and 4-aminobenzoic acid,2-aminoglutaric acid, Z-aminosuccinic acid, 3- and 4-aminophthalic acid,4- and S-aminoiso-phthalic acid and Z-aminoterephthalic acid;aminosulfonic acids, such as 2-amino and Z-methylaminoethanesulfonicacid, 3-amino-2-hydroxypropanesulfonic acid, 2-, 3- and4-aminobenzenesulfonic acid, 4-aminobenzene 1,3 disulfonic acid,Z-aminobenzene-l,4-disulfonic acid, 1-aminonaphthalene-4-, -5-, -6-, -7-and -8-sulfonic acid, 2-aminonaphthalene-5- or -6-sulfonic acid,l-aminonaphthalene-3,6-, -3,8- or -4,8-disulfonic acid,2-aminonaphthalene-4,8-, 5,7- or -6,8- disulfonic acid,l-aminonaphthalene-3,6,8-trisulfonic acid, 2 aminonaphthalene- 3,6,8-and 4,6,8- trisulfonic acid; low-molecular aminohydroxy compounds, suchas Z-hydroxyethylamine, 2- or 3-hydroxypropylamine,di-(Z-hydroxyethyl)-amine, di-(2- or 3-hyroXypropyl)-amine, methylamine,dimethylamine, ammonia, aminobenzene and N-methylaminobenzene. When Eand/or E represents a radical capable of dye formation, the reactionproduct is condensed with a suitable dye containing at least onesulfonic acid halide or carboxylic acid halide group, e.g. a copperphthalocyanine-trior-tetra-sulfonic acid chloride, or it is coupled witha diazonium salt to form a Water-soluble dye. The condensing or thecoupling reaction is performed in a weakly acid, neutral or alkalinemedium in the temperature range of from 0 C. to about 30 C., and withthe addition of an alkali, e.g. sodium acetate, carbonate orbicarbonate, in order to neutralize the mineral acid formed, e.g.hydrogen halide, sulfuric acid or sulfonic acid when the diazonium saltused contains a sulfonic acid group. Azo coupling is an importantreaction for the formation of the final dyes. It can be carried out byreacting a compound of Formula (II) with a compound of Formula (III)containing at least one readily acylatable amino group plus one poorlyacylatable but diazotizable amino group, diazotizing the intermediateand conpling the diazo compound with a coupling component to give awater-soluble dye. When diamines having two equally reactive aminogroups are employed, e.g. 1,3- or 1,4-diaminobenzene, it is best to workwith an excess of diamine to obtain the best possible yield of themonocondensation product and to prevent the second amino group frombeing condensed. Suitable coupling components are, e.g., phenolichydroxy compounds, such as monoand di-hydroxybenzenes, monoanddi-hydroxynaphthalenes which may be further substituted, e.g. withamino, acylamino, alkyl or alkoxy groups or halogen atoms, or in thecase of naphthalene derivatives with sulfonic acid groups enolic hydroxycompounds, such as pyr-azolones, acylacetylamino derivatives, preferably1- aryl-3-methy1- or 1 aryl-3-carboxy-5-pyrazolones, barbituric acid,acetoacetylaminoand benzoylacetylaminobenzenes and -naphthalenes whichmay be substituted with alkyl and alkoxy groups, halogen atoms, orpreferably sulfonic acid groups; compounds capable of reacting twicewith diazonium salts with formation of formazane dyes, e.g.cyclohexanone, levulinic acid, malonic acid derivatives, cyanaceticacid, acetylmethylsulfonyl-benzene or -naphthalene,carboxymethylsulfonylbenzene or -naphthalene and their sulfonic acids;amino compounds, such as aminobenzenes coupling in para position to theamino group, notably N,N-dialkylaminobenzenes which may be furthersubstituted; aminonaphthalenes which couple in the ortho position to theamino group and may be monoalkylated or monoarylated and may containfurther substituents, e.g. hydroxyl groups and/ or sulfonic acid groups,and S-aminopyrazoles.

Alternatively, a compound of Formula (II) can be condensed with certaincompounds of Formula (III) to yield an intermediate which can be used ascoupling component. The compounds of Formula (III) suitable hereto arethose containing at least one acylatable amino group plus a carbon atomcapable of coupling once or twice, e.g. aminohydroxy compounds such asaminohydroxybenzenes and -naphthalenes and their sulfonic acids,amino-enol compounds such as aminoarylpyrazolones,amino-acylacetylamino-benzenes and -naphthalenes and their sulfonicacids, and compounds capable of reacting twice with diazonium salts withthe formation of formazane dyes, such as aminocyclohexanone, 1-amino-3-and l-amino -4-carboxymethylsulfonyl-benzene or -napthalene and l-amino-3- or -4-acetyl-methyl-sulfonyl-benzene or -naphthalene.

E can denote the radical of a diazo component or of a couplingcomponent, which is similarly converted by azo coupling into the radicalof an azo dye. Examples of organic compounds suitable for the synthesisof the final reactive dyes are 1,3- and 1,4-diaminobenzenesulfonicacids, 1,3- and 1,4-diaminobenzenecarboxylic acids,4,4'-diamino-1,l'-diphenyl-3-sulfonic acid, l-(3- and 4'-amino)-phenyl-3-methyl 5 pyrazolones, aminohydroxynaphthalenes orpreferably their sulfonic acids, such asZ-amino-S-hydroxynaphthalene-7-sulfonic acid and -1,7- disulfonic acid,2-amino-8-hydroxynaphthalene-G-sulfonic acid and -3,6-disulf0nic acid,l-amino-8-hydroxy-naphthalene-4,6-disulfonic acid, orl-amino-S-hydroxynaphthalene-3,6-disulfonic acid.

The monoacylamino-monoamino compounds formed by monocondensation ofdiamines with a compound of Formula II can be converted into dyes by asecond condensation with e.g., an aldehyde with formation of a Schiffsbase or with an acid halide of a dye, preferably a carboxylic acidchloride or sulfonic acid chloride (copper phthalacyaninepolysulfonicacid chloride). Also, the products obtained by reactingamino-ketomethylene compounds, such as amino-pyrazolones andamino-acylacetylamino compounds with compounds of Formula II can becondensed with an aldehyde, preferably a substituted or unsubstitutedN,N-dialkylaminobenzaldehyde, to give styryl dyes.

A further mode of operation for the production of the new reactive dyesconsist in the reaction of 1 mole of a compound of the formula wherein Erepresents the radical of a water-soluble dye or of an organic compoundcapable of dye formation and R represents hydrogen or a substituted orunsubstituted alkyl radical, with 1 mole of a compound of the formula Nhal hal-O C wherein R represents hydrogen or a substituted orunsubstituted alkyl radical and R represents hydrogen or a substitutedor unsubstituted alkyl or aryl radical. When E stands for the radical ofa compound capable of dye formation, the reaction product is convertedinto a water-soluble dye by azo coupling or condensation. On completionof the reaction or of the condensation or coupling, the final reactivedye is precipitated from the solution or suspension which may bepreviously neutralized if preferredby the addition of sodium orpotassium chloride or an acid. It is filtered ofi with suction, washedand dried.

Interesting dyes of the Formula I are those, in which A represents theradical of a water-soluble monoazo dye, e.g. of the type:benzene-azomaphthalene or benzeneazo-S-pyrazolone or their 1:1-copper,1:1-nickel, 1:2- chromium or 1:2-c0balt complex compounds, polyazo dye,e.g. of the typei benzene-azo-benzene-azo-5-pyrazolone,benzene-azo-benzene-azo-naphthalene orbenzeneazo-naphthalene-azo-benzene and their metal complex compounds,anthraquinone dye, e.g. of the type l-amino- Z-sulfo 4phenylamino-anthraquinone, phthalocyanine dye, e.g. of the type:copper-phthalocyanine-di-or-trisulfonic acid, nitro dye, e.g. of thetype 2-nitro-1,l-diphenylamine-4-sulfonic acid-phenylamide, or formazanedye, e.g. the 1:1 copper complex compound of N,N-bis [2-hydroxy-4-(2'-carboxyphenylaminosulfonyl)-phenyl] ms (4"-amino-2",5"-dimethoxyphenylsulfonyl)-formazane, and A also representsthe radical of a monoazo dye, polyazo dye, anthraquinone dye,phthalocyanine dye, nitro dye or formazane dye e.g. of the typesmentioned above or of other types such as diphenyl-azo-naphthalene,benzeneazo-acetoacetylamino, naphthalene-azo-diphenyl-azo-benzene,naphthalene-azo-diphenyl-azo-naphthalene and their metal complexcompounds, A and A being identical or ditferen't from each other.Further interesting dyes of Formula I are those, in which one of thesymbols A and A represents the radical of a water-soluble monoazo dye,polyazo dye, anthraquinone dye, phthalocyanine dye, nitro dye orformazane dye, e.g. of the types mentioned hereinbefore, and the otherrepresents hydrogen, alkyl, preferably lower alkyl, which may besubstituted by hydroxy, alkoxy, halogen, e.g. chlorine, mononucleararyl, e.g. phenyl, carboxylic acid or sulfonic acid groups, orcarbocyclic aryl, preferably mononuclear or binuclear, which may besubstituted by lower alkyl, lower alkoxy, halogen, e.g. chlorine,carboxylic acid or sulfonic acid groups.

Of course the various dye classes represented by A plex compound ofN-(2-hydroxy-3,5-disulfopheny1)-N?- (4'-amino-2'-sulfophenyl) ms(4"-methylphenyl-sulfonyl)-formazane or ofN-(2-carboxy-4-sulfophenyl)-N'(4-amino-2'-sulfophenyl)-ms-butyryl-formazane or of N, N'-bis-(2-hydroxy5 aminosulfonylphenyl) ms (3"- amino-4"methoxyphenylsulfonyl)formazane.

Especially valuable dyes of the Formula I are those, in which Arepresents the radical of a blue water-soluble anthraquinone dye, e.g.of a l-amino-2-sulfo-4-arylaminoanthraquinone dye which may bearadditional SO H groups and/or halogen atoms, e.g. chlorine, lower alkylor lower alkoxy groups on the anthraquinone and/ or on the aryl nucleus,and A represents also the radical of a blue water-soluble anthraquinonedye, or the radical of a water-soluble monoazo, disazo or nitro dye, sothat the final dye possesses a shade which may vary from violet to blueand to green according to the shade of the monoazo, disazo or nitro dyeemployed, or A represents the radical of a water-soluble phthalocyaninedye or formazane dye of the types described above and A represents theradical of a water-soluble monoazo, disazo or nitro dye or A representsthe radical of a water-soluble monozao, disazo or nitro dye, e.g. of abenzene-azo-naphthalene or benzene-azo-S-pyrazolone dye, of abenzene-azo-benzeneazo-naphthalene orbenzene-azo-naphthalene-azo-benzene orbenzene-azo-benzene-azo-S-pyrazolone dye or a 2-nitrodiphenylamine dye,these dyes bearing 1 to 4 water-solubilizing groups, and A representsthe radical of a watersoluble anthraquinone, phthalocyanine or formazanedye of one of the types mentioned above.

IThe new reactive dyes which contain three or more water-solubilizinggroups, such as carboxylic acid groups, sulfonic acid amide groups or,preferably, sulfonic acid groups, possess good solubility in water, goodcompatibility with salts and hard water, and good reactivity withcellulosic fibers, animal and synthetic polyamide fibers. They reserveacetate, triacetate, polyester, acrylic, polyvinyl chloride, polyvinylacetate and polyalkylene fibers. Owing to their good aqueous solubility,the unfixed residue of dye on printed or dyed cellulosic fiber materialscan be easily removed by washing.

Those reactive dyes of the invention which contain only one or twowater-solubilizing groups, preferably sulfonic acid groups, are highlysuitable for the exhaustion dyeing of cellulosic fibers and for the aciddyeing of wool, silk and synthetic polyamide fibers.

Beside the number of water-solubilizing groups the substantivity is asignificant factor for the properties of the new dyes. When one of theconstituents of the dyeis a group like:

3 'SOaH it is more substantive than a corresponding dye having a grouplike the following:

Q QN

In the formulae X, represents in both positions a hydrogen atom or ahalogen atom, or a methyl, methoxy, ethoxy or SO H- group, oralternatively one X represents a hydrogen atom and the other --SO H; Xin both positions represents a halogen atom, or a methyl, methoxy,ethoxy or -SO H group; Y represents a hydrogen atom, a low-molecularalkyl group or a phenyl group which may be substituted by alkyl oralkoxy groups; and the arrow denotes the coupling position in theaminohydroxynaphthalenesulfonic acids.

The introduction of an additional water-solubilizing group, e.g. an -SOH group, normally results inhigher solubility in water and a reductionin the affinity for cellulosic fibers. But when the dye contains asubstantive group as well as an additional SO H group, it has theincreased solubility in water but does not lose its good affinity forcellulosic fibers. Hence dyes with, for instance, three -SO H groups canbe employed for exhaustion dyeing provided they also contain one or moresubstantive groups.

In comparison with the dyes of Formula (11) used as starting products,the final dyes show considerably higher storage stability both in powderform and in solution in padding liquors and printing pastes. Moreoverall desired shades, in particular the intermediate tones, such as green,violet, orange and scarlet, can be produced in a simple way by combiningtwo different chromophores.

The new reactive dyes are suitable for dyeing leather and for dyeing,padding and printing fibers of animal and vegetable origin, fibers ofregenerated cellulose, caseln fibers, anim-alized cellulose fibers, andsynthetic polyamide fibers, and also blended materials consisting of theaforestated fibers.

The optimum conditions of application vary with the type of fiber andthe particular dyes used. Animal fibers and synthetic polyamide fibersare dyed, printed or fixed preferably in an acid, neutral or weaklyalkaline medium, e.g. in the presence of acetic, formic or sulfuricacid, ammonium sulfate, sodium metaphosphate etc. The dyes can beapplied from an acetic acid to neutral medium in the presence of aleveling agent, e.g. polyoxethylated fatty amines or mixtures of theseand alkylpolyglycol ethers, and the bath adjusted to a neutral or weaklyalkaline reaction at the end of the operation by the addition of smallamounts of an agent of alkaline reaction, e.g. ammonia, sodium carbonateor bicarbonate, or of compounds which react alkaline on heating, e.g.hexamethylene-tetramine or urea. Subsequently the goods are rinsed welland acidified with acetic acid.

In the dyeing and printing of textile materials made of animal orsynthetic polyamide fibers the chemical linkage between the dye moleculeand the fiber is often less pronounced than otherwise, depending on thereowes its affinity for the fiber partly to its acidic character. Thedyeings on Wool and synthetic polyamide fibers have good light fastnessand excellent fastness to perspiration, washing, water, sea water,milling and dry cleaning.

The dyeing, padding and printing or fixation of the dyes on cellulosicfibers is carried out in alkaline medium, e.g. in the presence of sodiumcarbonate or bicarbonate, sodium or potassium hydroxide, sodiummetasilicate, sodium borate, trisodium phosphate, ammonia, etc. Toprevent reduction effects, it is often of advantage to add a mildoxidizing agent, such as sodium-3-nitrobenzenel-sulfonate to thedyebath, padding liquor or printing paste. In contrast to the startingcompounds of Formula (II), which are cold-dyeing types, the final dyesare socalled hot-dyeing brands and are normally fixed on cellulosicmaterials with heating. Provided a sufiiciently strong alkali is used,such as sodium or potassium hydroxide or sodium silicate, and a storagetime of 24 hours or more is allowed, fixation can be effected attemperatures of 20 to 40 C.

The dyeings and prints on cellulosic fibers are outstandingly fast towet treatments (washing, water, sea water, perspiration) as well as torubbing, alkali, acetic acid cross-dyeing, and dry cleaning, and highlyresistant to alkaline hydrolytic influences. These properties are due tothe formation of a stable chemical linkage between the dye molecule andthe cellulose molecule. Often the entire amount of dye applied to thefiber does not participate in the reaction; the unreacted residue isremoved from the goods by suitable treatment, such as rinsing and/orsoaping, if necessary at high temperature, for which purpose syntheticdetergents can be used, e.g. alkylarylsulfonates such as sodiumdodecylbenzenesulfonate, alkylsulfates such as sodium lauryl sulfate,optionally sulfated or carboxymethylated alkyl-polyglycol, monoalkylanddialkyl-phenylpolyglycol ethers such as sodium lauryl polyglycol ethersulfate, and sodium lauryl polygyco ether acetate.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

Example 1 28 parts of 4amino-1,1-azobenzene-4'-sulfonic acid aredissolved in 500 parts of water at 20-30 with the addition of sufficientdilute sodium hydroxide solution to obtain the pH value 8.5. 71 parts ofthe sodium salt of condensation product of 1-amino-4(3'-amino)-pheny1-aminoanthraquinone-2,4'-disulfonic acid and2,4-dichloropyrimidine-S-carbonyl chloride are strewn into the solutionin the course of 1 hour with the addition of further dilute sodiumhydroxide solution to maintain the pH at 7.5-8.5. When chromatography ofa sample of the reaction mixture shows that no further startingsubstance is present, 70 parts of sodium chloride are added toprecipitate the dye. It is filtered off and vacuum dried at 60. A darkgreen powder is obtained which dyes cotton from aqueous solution ingreen shades having very good light and excellent wet fastness. The dyehas the formula:

NH u ol 8 OaNa 'soaNa Dyeing meth0d.1.5 parts of the dye of Example 1are dissolved in 4000 parts of softened water at 40. 100 parts ofmercerised cotton fabric are entered into this bath. Then 110 parts ofcalcined sodium sulfate and 30 parts of calcined sodium carbonate areadded. The bath is raised to 100 in 30 minutes, with the addition afterthe first minutes of 110 parts and after minutes of 100 parts ofcalcined sodium sulfate. When 100 is reached, 50 parts of calcinedsodium carbonate are added and this temperature is maintained for 1hour. The goods are rinsed with cold and warm water, soaped at the boilfor 10-20 minutes with a 2 g./l. solution of an alkylpolyglycol ethersulfate, rinsed well and dried. A green dyeing fast to light and wettreatments is obtained.

Example 2 17.5 parts of l-aminobenzene-3-sulfonic acid and 71 parts ofthe sodium salt of the condensation product of 1 amino 4 (3' amino)phenylaminoanthraquinone- 2,4-disulfonic acid and2,4-dichloropyrimidine-S-carbonyl chloride are stirred into 500 parts ofwater at 20-25". The pH of the mixture is adjusted to 7.5 with dilutesodium carbonate solution and it is maintained at this value for 2 hourswith the addition of further sodium carbonate solution if necessary.When chromatography of a sample of the reaction mixture indicates thatno further starting material is present, 50 parts of sodium chloride areadded to precipitate the dye. It is filtered ofl, washed with dilutesodium chloride solution, vacuum dried at 5060 and ground. A dark bluedye in which has the formula i)' NHGNH I This dye dissolves in water togive brilliant blue solutions powder form is obtained and dyes cottonfrom aqueous solution in brilliant blue shades.

Printing meth0d.Mercerised cotton fabric with a paste of the followingcomposition:

is printed Parts Dye of Example 2 30 Urea Water 395 3% sodium alginatethickening 450 Sodium-l-nitrobenzene-3-sulfonate 10 Sodium carbonate 15Total 1000 The fabric is dried, steamed for 10-15 minutes at 102- 104",rinsed with cold and warm water, soaped at the boil, rinsed again anddried. A blue print is obtained having very good wet fastness propertiesand excllent light fastness.

Example 3 71 parts of the yellow dye of the formula into the mixture,causing the dye to be precipitated. It is filtered oil? and dried. Thegreen dye has the formula SO Na SOaNa 1x and dyes cotton in yellowishgreen shades of good light and excellent wet fastness.

Padding method-3 parts of the dye of Example 3 ar dissolved in 100 partsof warm water, and 30 parts of 10% sodium carbonate solution and 0.5part of sodium- 1-nitrobenzene-3-sulfonate are added. This solution ispadded on a fabric of viscose staple fiber, which is then expressed toan increase of 75% over its dry weight, dried, steamed in wet steam for5 to minutes at 102, rinsed with warm and cold water, soaped at the boilif necessary with subsequent warm and cold rinsing, and finally dried. Ayellowish green dyeing is obtained having very good washing and lightfastness.

Example 4 37 parts of the condensation product of sodium-3- aminobenzenesulfonate and 2,4-dichloropyrimidine-5-carbonyl chloride are dissolvedin 600 parts of water at about In the course of 2 hours 53 parts ofsodium-l-amino- S OaNa 4-(4-amino)-phenylaminoanthraquinone 2,6disulfonate are added with simultaneous dropwise addition of dilutesodium carbonate solution to maintain the pH of the mixture at about 8.On completion of condensation 50 parts of sodium chloride are added, theprecipitated dye filtered off, washed with dilute sodium chloridesolution and dried. The dye is a dark blue powder which dissolves inwater with a greenish blue coloration; it has the formula NHg -S OaNaWhen the 37 parts of the condensation product of sodium-3-amino-benzene-sulfonate and 2,4-dichloropyrimidine-5- carbonylchloride in the above example are replaced by 71 parts of thecondensation product of sodium-l-amino-4-(4-amino)-phenyl-aminoanthraquinone 2,6 disulfonate and2,4-dichloropyrimidine-S-carbonyl chloride and the procedure of thisexample followed, a similar dye is obtained which, however, is ofsubstantive character.

are dissolved in 3000 parts of water at and the pH value adjusted to 8.A neutral solution of 19.5 parts of sodium-1-amino-benzene-3-sulfonatein 200 parts of water is added and the pH value kept at 7.5-8.5 bydropping in 20% sodium carbonate solution. When the chro- 12 matogram ofa sample of the reaction mixture shows that no further starting materialis present, the dye is precipitated by the addition of potassiumchloride. It is filtered with suction, vacuum dried at 60 and ground togive a yellow powder which dyes cotton by the method of EX- ample l inyellow shades.

Example 6 A solution of 74.1 parts of the yellow dye (XI) in 3000 partsof water is prepared as described in Example 5, and at 2830 a neutralsolution of 46.7 parts of sodium-1-hydroxy-2-phenylazo-6-aminonaphthalene 3,2 disulfonate in 500 parts ofwater is added to it. The pH value is maintained at 7.58.5 by dropwiseaddition of 20% sodium carbonate solution until the yellow starting dyeis no longer indicated by chromatography. The orange disazo dye of theformula -S OaNa CH (XII) is precipitated by the addition of salt,filtered with suction and dried. It is obtained as an orange-brownpowder which dissolves in water with an orange coloration, It givesorange dyeings and prints on cellulosic fibers which are fast to wettreatments.

SO3Na Example 7 41 parts of the dye to the formula S OaNa (X III) M3,342,797 13 a l 14 Q Example 8 in the form of a green powder, whichdissolves in watei' with a green coloration and dyes cotton in brilliantgreen parts of the dye of the fPTmUIa shades having very good light andwet fastness.

A dye with similar properties is obtained when 4.5

N parts of the compound (HOzSh-CuPC-SOzNH- NHC 431 N N=N NH:

CH3 -son 1 l 3 (XIV) N CE are stirred into 200 parts of water, 1.9 partsof l-aminobenzene-3-sulfonic acid added, and the pH value of the Clmixture ad usted to 8.0-8.5 W1th sodium carbonate solution. It is thenheated to 30-35" with slow addition of 01 further sodium carbonatesolution to maintain the pH at 8.0-8.5. When the pH remains stable atthis value without 1 so H 5 1 any further addition, the condensationreaction 1s comare condensed with 112 parts of the dye of formulapleted. The dye is precipitated by the addition of sodium chloride,filtered with suction, washed with sodium chloride solution, vacuumdr1ed at 6Q and ground. The dye (HOSS)3 CHPC SO:NHCHCHNHAJO is obtainedas a black powderwhich dissolves in water to give blue solutions anddyes cotton in brilliant turquoise (XXI) shades. It has the formulaunder the same conditions.

'N lol (NaOsS)aGuPCSOzNH NH-CO N -SOaNa some J y With Similar Propertiesare Obtained when T e following table gives details of further dyeswhich parts of the compound f th formula can be produced according tothe procedures of Examples s oaH c1 l to 9 and which correspond to theformula N -N1-I-C 0- 01 Z G N 1. SO3H Z1 (XVI) I o(] I wherein Zrepresents CH or 4.8 parts of the compound -N I of Formula XVI wherein Zrepresents a mixture of CH R, CH Cl and CHCl are condensed with 11.7parts of the 40 dye of th fo m la They are defined in the table -by theconstitutions of the radicals (HO;S)iCuPCSOr-NH NH,

A1-NH and .Al-NH xvn under the same conditions. A

Example -9- in each of which the amino group is underlined, by the 12.4parts ofv the dye of Formula XIV are stirred into mdical 100 parts ofwater, to which are added 4.6 parts of the yellow dye of the formula 1 pfrom which the radical (XVIII) z hal The condensing-reaction is carriedout according to the I particulars given inExample 8. It yields a dye ofthe formula I i S l 6 is derived, and by the shade of the dyeing orprint on are given, in the second shade of the dyeing or print oncotton. The table is divided into three parts: in the first cotton, andin the third the starting radicals part the chemical designations of theradicals U for the final dyes.

TABLE I.PART 1 Ex. No. R R:

- i-amino-i-(4-aminophenyiamin0)- 1-(2,5-dichloropheny1)-3-rnethy1-4-anthraquinone-2,%-disulionic acid. (3-aminophenylazo)-5-pyrazolone-4-suiionic acid.

11 1-(2,5-dichlorophenyl)-3-methyl-4- l-amino-i-(4-arninophenyl-amino)-(3"-aminophenylazo)-5-pyrazoloneanthraquinone-2,G-disulionic acid.4,6-disulionic acid.

12 l-aminoi-(3-aminophenyiamino)- 1-amino-4-(3-arninophenylamino)-anthraquinone2,4-disulionic acid. anthraquinonc2,4-disulionic acid.

1-amin0benzene-2,5-disulionic acid. Do.

1-arnino-4-(3-amino-4-methyi- 1-(2,5-dichlorophenyl)-3-methyi-4-phcnylarnino)-anthraquinone,2,6,6-(3-aminophenylazo)-5-pyraz0ionetrisulionic acid. 4,6-disulionic acid.

15 l-amino-4-(3-arnin0phenylamino)- 1(2-methylphenyi)-3-methyl-i-(3-anthraquinone-2,4-disulionic acid. aminophenylazo)-5-pyrazolone-4,6-disulionic acid.

16 1-aminobenzene 3-sullonic acid Do.

17 i-phenyl-3-methy1-i-(3-aminol-aminoi-(4-aminophenylamin0)-phenylazo)-5-pyrazolone-2 ,5-disulanthraquinone-2,2-disulionic acid.ionic acid.

18 l-amino-3-methyl-4-(4-phenyiazo)- Do.

phenylazo)-benzeue-2 ,4 -disul- Ionic acid.

19 do 1-amino--i-(4-methyiaminophenylamino)-anthraquinone-2,2-disulionicacid.

20 i-amino-i-(3-aminophenylarnino)-1-pheny1-3-methyl-4-(3"-aminophenylanthraquinone-2,7,4-trisulionicazo)-5-pyrazolone-2,5-disuiionic acid. acid.

do Do.

l-aminoi-(4'-aminophenylamino)- l-aminobenzene-4-suiionic acid.

anthraquinone-Z,7-disulionic acid. .do Do.

i-amino i-(4-aminophenylamino)- l-amino-4-(4-aminophcnylamino)-anthraquinone-2,7-disulionic acid. anthraquinone-2,7-disulionic acid.1-amino-4-(4-aminopheny1amino) 1-(2-methylphenyi)-3-methyi-4-(3"-anthraquinone-2,%disulionic aminophenylazo)-5-pyrazo1oneaci4,6"-disu1ionie acid.

26 1-aminobenzene-2,5-disulionic acid. 1-aruin0-4-[4-(4"-aminopheny1)-phenylamino]-anthraquinone-2,6,3"- trisulionic acid.

27 2-(4-amino-2-methylphenylazo)- Bis-(Q-hydroxyethyD-amino.

naphthalene-4,8-disullonic acid. do Z-aminoethanesulionic acid.

1-l1ydroxy-2-(4-methyiphenylazo)- Z-aminobenzene-l-carboxyiic acid.

S-aminonaphthalene-3,6,2-trisulionic acid.

30 i-hydroxy-Z-pheny1az0-8-amin0- Methylaminoacetic acid.

naphthalene-3 6,2-trisulionic acid.

Z-aminoethanol. 2-(4-amino-2-rnethylphenylazo)-naphthalene-4,B-disulionic acid. 1-amino-4-(4'-aminophcnylan1ino)-anthraquinone-Z,fi-disulionic acid.

34 112-cobalt complex compound 0! 1- Mathylamine.

(2-hydroxy-5-nitrophenylazo)-Z- hydroxy-Ii-aminonaphthalene-7,3-

disulionic acid. 35 ..do 1-amino-3-methoxypropane. 36 1:2-chromium ex cound oi i-aminopropanol-2.

1-hydroxy-2-(2-hydroxy-5-chlorophenyiazo) 8-aminonaphthaiene-3,6-disu1ionic acid.

37 1:2-chromiurn complex compound oi lzz-cobalt complex compound oi 1-l-hydroxy-Z-(2-hydroxy-5-nitrohydroxy-2-(2hydroxy-5-nitrophenyiazo)-8-aminonaphtha1enephenylazo)-8-aminonaphthaiene-3,6-disuii0nlc acid. 3,6disulionic acid.

38 Copper complex compound oi 1- l-amino-n-butane.

4,3-disulionic acid. 41 ..do i-aminobenzene-S-sulionic acid.

1 7 1 8 TABLE I.-PART 2 in Examples 10 to 18, 21, 26, 2s, 32, 33, and 35to 39,

Shade of dyeing and H Example: print on cotton I v i N green --OC -B1 11Do. I N

12 reddish blue l3 greenish blue 14 green in Examples 19 and 31, 15 Do.10 CH 16 yellow f 17 green C1 18 olivegreen 19 Do. 20 7 green 15 C 21Do. 22 greenish blue in Examples 22, 24 and 25, 23 Do. 24 Do; 20 h z 25green N 26 Do. -oo -c1 27 yellow 28 Do. 01 29 red 25 v 30. v red I inExamples 20, 23, 29, 30, 40 and 41 (Where Z is a mix- Rd ture of CH CHCI and CHCI 32 scarlet 33 violet 34 brown 35 I Do. o C B 36 navy blue r.1 -2 black v3. violet 39 I red 35 I 4 I I orange 1n Example 27 and 41red z,

I I 0c 131- The radical I I I Y a Br ' N in Example 34 (where Z is amixture of CH CH Br 4181 V and CHBr II N I 45 Formulae of representativedyes of the foregoing exam- 1181 I ples'are as follows: r

I Example 5 01 OH Cl KO S-GN I N I I N= 'NH-OC 1 01 N N v CH: KOQS- I iI v SIO3K from which the radical Example 7 Z i N lhal r 20 is derived,is

Example 12 ('1') NH: "I

S O Na NaO S Having thus disclosed the invention what I claim is: 1.Reactive dyes of the formula l R1 E2 wherein hal is a member selectedfrom the group consisting of chlorine and bromine,

R is a member selected from the group consisting of hydrogen, loweralkyl, lower hydroxyalkyl, (lower) alkoxy (lower) alkyl and lowerphenylalkyl,

R is a member selected from the group consisting of hydrogen, loweralkyl, lower hydroxyalkyl, (lower) alkoxy (lower) alkyl and lowerphenylalkyl,

Z is a member selected from the group consitsing of hydrogen, chlorine,bromine, CH CH CI, CHCI CHZBI' and CHBI'Z,

A is a member selected from the group consisting of hydrogen, loweralkyl, lower hydroxyalkyl, (lower) alkoxy (lower) alkyl, lowercarboxyalkyl, lower sulfoalkyl, lower dicarboxyalyl, lower phenylalkyl,phenyl carboxyphenyl, dicarboxyphenyl, sulfophenyl, disulfophenyl,sulfonaphthyl, disulfonaphthyl, the radicals of monoazo dyes, disazodyes, lzl-copper and 1:1 nickel, complex azo dyes, 1:2-cobalt complexazo dyes, 1:2-chromium complex azo dyes, anthraquinone dyes,phthalocyanine dyes, nitro dyes and formazane dyes, the said dyeradicals bearing 1 to 4 water-solubilizing groups selected from thegroup consisting of -SO H, SO -NH and COOH, and

A is a member selected from the group consisting of hydrogen, loweralkyl, lower hydroxyalkyl, (lower) alkoxy (lower) alkyl, lowercarboxyalkyl, lower sulfoalkyl, lower dicarboxyalkyl, lower phenylalkyl,phenyl, carboxyphenyl, dicarboxyphenyl, sulfophenyl, disulfophenyl,sulfonaphthyl, disulfonaphthyl, the radicals of monoazo dyes, disazodyes, 1:1-copper and 1:1 nickel, complex azo dyes, 1:2-cobalt complexazo dyes, 1:2-chromium complex azo dyes, anthraquinone dyes,phthalocyanine dyes, nitro dyes and formazane dyes, the said radicalsbearing 1 to 4 water-solubilizing groups selected from the groupconsisting of SO H, SO --NH and COOH, at least one of A and A being adye radical.

2. Reactive dyes of the formula N -hal Al-N-OO i -N-A;

wherein hal is a member selected from the group consisting of chlorineand bromine,

R is a member selected from the group consisting of hydrogen, loweralkyl, lower hydroxyalkyl, (lower) alkoxy (lower) alkyl and lowerphenylalkyl,

R is a member selected from the group consisting of hydrogen, loweralkyl, lower hydroxyalkyl, (lower) alkoxy (lower) alkyl and lowerphenylalkyl,

Z is a member selected from the group consisting of hydrogen, chlorine,bromine, CH CH CI, CH Br and CHBr A is a member selected from the groupconsisting of hydrogen, lower alkyl, lower hydroxyalkyl, (lower) alkoxy(lower) alkyl, lower carboxyalkyl, lower dicarboxyalkyl, lowersulfoalkyl, lower phenylalkyl, phenyl, carboxyphenyl, dicarboxyphenyl,sulfophenyl, disulfophenyl, sulfonaphthyl, disulfonaphthyl, the radicalsof benzene-azo-benzene dyes, of benzene-azo-naphthalene dyes, ofbenzene-azo-S-pyrazolone dyes, of benzene-azo-barbituric acid dyes, ofbenzene-azo-acetoacetylamino dyes, of naphthaleneazo-naphthalene dyes,of naphthalene-azo-S-pyrazolone dyes, of naphthaleneazo-acetoacetylaminodyes, of diphenyl-azo-naphthalene dyes, of diphenylazo-S-pyrazolone dyesand of pyrene-azo-benzene dyes, the said monoazo dyes bearing 1 to 4 -SOH groups, the radicals of the lzl-copper, lzl-nickel, 1:2- chromium and1:2-cobalt complex compounds of the aforesaid monoazo dyes, the radicalsof benzene-azo-benzene-azo-benzene-dyes, of benzene-azobenzene-azo-naphthalene dyes, of benzene-azo-benzene-azo-S-pyrazolonedyes, of benzene-azo-naphthalene-azo-benzene dyes, ofnaphthaleneazo-diphenylazo-benzene dyes, ofnaphthalene-azo-diphenyl-azonaphthalene dyes and ofnaphthalene-azo-naphthalene-azo-naphthalene dyes, the said disazo dyesbearing 2 to 4 -SO H groups, the radicals of the 1:1- copper,lzl-nickel, 1:2-chromium and 1:2-cobalt complex compounds of theaforesaid disazo dyes, the radicals of1amino-2-sulfo4-arylaminoanthraquinone dyes having a total of from 2 to3 SO H groups and wherein the aryl is hydrocarbon and from mononuclearto binuclear, the radicals of copperphthalocyanine andnickel-phthalocyanine dyes containing from 2 to 4 water-solubilizingsubstituents selected from the group consisting of -SO H and SO NH theradicals of 2-nitro-l,1'-diphenylamino dyes bearing 1 to 2 --SO H groupsand the radicals of metal-containing formazane dyes with 1 to 3 SO Hgroups, and

A is a member selected from the group consisting of and 1:2-cobaltcomplex compounds of the aforesaid monoazo dyes, the radicals ofbenzene-azo-benz ene azo benzene dyes, of benzene azo benzeneazonaphthalene dyes, of benzene-azo-benzene-azod-py-' razolone dyes, ofbenzene-azo-naphthalene-azo-benzene dyes, ofnaphthalene-azo-diphenyl-azo-benzene dyes, ofnaphthalene-azo-diphenyl-azo-naphthalene dyes and of naphthalene azonaphthalene azonaphthalene dyes, the said disazo-dyes bearing 2 to 4 -SOH groups, the radicals of the Ill-00131361, 1 1-- nickel, 1:2-chromiumand 1:2-cobalt complex compounds of the aforesaid disazo dyes, theradicals of I N O NH NH-O C- SO;Na

S O NB OH NaO S N l N I 01 N N NaOS (S OaNa):

CuP C-S Or-NH S OaNa I NH 4 3. The reactive dye of the formula H'1-amino-2-sulfo-4-arylaminoanthraquinone dyes having a total of from 2to 3 -S0 H groups and wherein the aryl is hydrocarbon and frommononuclear to binuclear, the' radicals of copper-phthalocyanine andnickel-phthalocyanine dyes containing from 2 to 4 water-solubilizingsubstituents selected from the group consisting of SO H and SO -NH theradicals of 2-nitro-1,1'-diphenylamine dyes bearing 1 to 2 SO H groupsand the radicals of metal-containingjormazane dyes with 1 to 3 SO Hgroups, at least one ofA and A; being a dye radical.

4. The reactive dye of the formula BOJNB s OaNa -HN SOaNa 5. Thereactive dye of the formula NH; O I ll -01 NaOaS SO3N8 TEN-GEN 0 6. Thereactive dye of the formula CI-L SOaNa N NHONH[ 4: 0--HN SOsNa 7. Thereactive dye of the formula (References on following page) ReferencesCited UNITED STATES PATENTS 1,667,312 4/1928 Fritzsche et a1. 260-153FOREIGN PATENTS 221,678 6/1962 Austn'a. 1,247,660 10/1960 France.

CHARLES B. PARKER, Primary Examiner.

F. HIGEL, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,342,797 September 19, 1967 Jacques Guenthard It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 1, line 55, for "formula" read formulae line 58, for "and", firstoccurrence, read or line 65, for "i.g." read e.g. line 69, after "amino"insert group column 2, line 24, before "ms" insert a hyphen; line 28,for "chrominum" read chromium column 3, line 4, for "is is" read it islines 9 and 10, should appear as shown below instead of as in thepatent:

-S02NH-CH2CH2- or -SO2-NH-O' lines 34 to 35, after the formula insert aperiod; column 4,

line 45, for "-naptha1ene" read naphthalene column 5, line 1, for"consist" read consists column 6, line 6, for"amino-4methoxyphenylsulfonylJ formazane" read amino-4-methoxyphenylsulfonyl)formazane line 22, for "monozao" read monoazocolumn 8, lines 51 and S2, for "polygyco" read polyglycol column 9, line36, for "2,4-disulfonic" read 2 ,4 -disulfonic same column 9 formula [VII), for

that portion of the formula reading:

N read N column 11, formula (X) should appear as shown below instead ofas in the patent:

/ CO-NH SO Na column 12, formula (XIII) the upper right-hand portion ofthe formula should appear as shpwn below instead of as in the patent:

same column 12, line 72, for "wtih" read with column 16, line 1, after"second" insert the columns 15 and 16, TABLE 1, Ex. No. 10, firstcolumn, line 1, for V-amino" read 4 -amino line 2 for "2, /a" read 2,5/8second column, line 2, for "B -amino" read S' -amino EX. No. 11, firstcolumn, line 2 for "3-amino" read 3 -amino second column, line 1, for "4amino" read 4 -am1no Ex. No.

12, first column, line 1, and second column, line 1, for "3 amino", eachoccurrence, read 3 -amino Ex. No. 13, first column, line 1 for "1amino." read l-amino Ex. No. 14 first column, line 1 for "Z g amino"read 3 amino second column, line 2 for "V -amino read E -amino Ex. No.15 second column, lines 1 and 2 for "3 -amino" read 3amino Ex. No. 17,first column, line 1, for "3"amino" read 3 amino w; Second column, line1, for "4 amino" read 4 amino EX. No. 18, first column, line 1, for"l-amino" read l-amino '5 Ex. No. 19, second column, line 1, for"methylamino" read meth lamino EX. No. 20, first column, line 1, for "3amino" read 3 -amino second column, line 1, for "3 amino" read 3' -aminoEx. No. 22 first column, line 1 for "4 amino" read 4 -amino secondcolumn, line 1, for "l'aminobenzene" read l-aminobenzene Ex. No. 23,second column, line 1, for "Do" read laminobenzene-4-sulfonic acid H;Ex. No. 24, first column, line 1, and second column, line 1, for "4amino", each occurrence read 4 -amino Ex. No. 25 first column, line 1,for l -amino" read 4 -amino same column 1, line 2 for "2 /s" rad 2 ,5/8second column, line 2 for "aminophenylazo" read aminophenylazo Ex. No.26, first column, line 1, for "aminobenzene" read aminobenzene EX. No.27, first column, line 1, for "amino" rea H amino second column, line 1,for

"amine" read amine Ex. No. 28, second column, line 1, for "amino" readamino Ex. No. 29, first column, line 2, and second column, line 1, for"amino", each occurrence, read amino Ex. No. 30, first column, line 1,for "amino" read amino second column, line 1, for "Methylaminoacetic"read Metfi laminoacetic Ex. No. 31, second column, line 1, foramdnoetfianol" read aminoethanol Ex. No. 32, second column, line 1, for"amino" read amino Ex. No. 33, second column, line 1, for"aminophenylamino' read aminophenylamino Ex. No. 34, first column, line3, for "aminonaphthalene" read H aminonaphthalene second column, line 1,for "Methylamine" read Meth lamine Ex. No. 35, second column, line 1,for "amino" read amlno Ex. N0. 36, first column, line 3, and secondcolumn, line 1, for "amino", each occurrence, read amino EX. No. 37,first column, line 3, and second column, lin 3, for "aminonaphthalene",each occurrence, read aminonaphthalene Ex. No. 38, first column, line 3,and second column, line 1, for "amino", each occurrencenread amino Ex.No. 39, first column, line 2, and secondcolumn, line 1, for "amino",

each occurrence, read amino Ex. No. 40, second column, line 1, for"aminophenylazo" read amino henylazo Ex. No. 41, second column, line 1,for "aminoB enzene" read aminobenzene column 19 line 38 for"dicarboxyalyl" read dimxyalkyl column 20, line 64, for "pheny" readphenyl columns 21 and 22, claim 6, the right-hand portion of the formulashould appear as shown below instead of as in the patent:

Same columns 21 and 22, claim 8, the right-hand portion of the formulashould appear as shown below instead of as in the patent:

c1 2 N N O S N a 3 NH HN O NaO S This certificate supersedes Certificateof Correction issued January 14, 1969.

Signed and sealed this 18th day of November 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

1. REACTIVE DYES OF THE FORMULA